US3801588A - Certain perfluoroalkylsulfon-amidothiazoles - Google Patents

Certain perfluoroalkylsulfon-amidothiazoles Download PDF

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US3801588A
US3801588A US00142381A US3801588DA US3801588A US 3801588 A US3801588 A US 3801588A US 00142381 A US00142381 A US 00142381A US 3801588D A US3801588D A US 3801588DA US 3801588 A US3801588 A US 3801588A
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compounds
salts
imidazo
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V Heights
J Robertson
J Harrington
D Kvam
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Pbi-Gordon Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C07D277/52—Nitrogen atoms bound to hetero atoms to sulfur atoms, e.g. sulfonamides

Definitions

  • salts of these compounds are also included.
  • compositions containing the compounds of the present invention are also included.
  • the compounds are active as herbicides and plant growth modifiers.
  • the invention relates to perfiuoroalkanesulfonamides, N-substituted by heterocyclic ring-containing groups, said compounds having activity as herbicides and plant growth modifiers, and particularly as preemergence herbicides.
  • Perfluoroalkanesulfonamides have been disclosed broadly heretofore (see, for example, US. Pats. 2,732,398 and 3,321,445) but there has been no indication of any herbicidal activity of such compounds.
  • the sulfonamide nitrogen substituent is a heterocyclic ring-containing group selected from pyridinyl, quinolinyl, pyrazolyl, thiazolyl, quinoxalinylphenyl, imidazo[1,2a] pyridinylphenyl, imidazo[l,2a] pyrimidylphenyl and benzoxazolyl, said groups being unsubstituted or substituted.
  • the invention also includes salts of the compounds, processes for their preparation, compositions containing them and methods for their use as herbicides, and plant growth modifiers.
  • R is a perfluoroalkyl group containing one to four carbon atoms
  • Het is selected from pyridinyl, quinolinyl, pyrazolyl, thiazolyl, quinoxalinylphenyl, imidazo- 1,2a] pyridinylphenyl, imidazo[ 1,2a] pyrimidylphenyl and benzoxazolyl
  • Y is lower alkyl, halogen, cyano, lower alkoxy, nitro, amino or lower alkanolylamido
  • n is 0- 2 when Het is thiazolyl and is otherwise 03.
  • n When n is zero, the Het group in the compound is not substituted by any Y groups, i.e. hydrogen appears in place of the Y groups.
  • the compounds of the invention in which n is 0 or, in which n is 1 form preferred classes of compounds of the invention.
  • the sulfonamide hydrogen of the formula is replaced by a suitable cation.
  • the salts of the invention are prepared by treating the acid form (shown in the foregoing Formula I) with a stoichiometrically equivalent amount of an appropriate base under mild conditions.
  • the metal salts of the invention are alkali metal (e.g. lithium, sodium and potassium), alkaline earth metal (e.g. barium, calcium and magnesium) and heavy metal (e.g. zinc and iron) salts as well as other metal salts such as aluminum.
  • Appropriate bases for use in preparing the metal salts include metal oxides, hydroxides, carbonates, bicarbonates and alkoxides. Some salts are also prepared by transmetallation reactions.
  • the organic amine salts include the salts of alkylamines and aromatic amines, primary, secondary or tertiary.
  • ammonium salts can be prepared by reacting the acid form with the appropriate organic base or ammonium hydroxide.
  • the salts of the invention are frequently formed by reacting the precursors in aqueous solution. This solution can be evaporated to obtain the salt of the compound usually as a dry powder. In some cases, it may be more convenient to use a non-aqueous solvent such as alcohols, acetone, etc. Since many of the salts are water soluble, they are often used in the form of aqueous solutions.
  • the compounds of the invention are catalysts for certain acid-catalyzed polymerizations.
  • Many of the compounds of the invention are anti-microbial agents, according to standard test procedures. Also, some are anti-inflammatory agents when tested by standard test procedures using animals.
  • R in the compounds of the invention is trifiuoromethyl.
  • Price is an important consideration in herbicides and such compounds offer more economical utilization of fluorine together with high activity.
  • the group Het-Yn in the compounds usually and preferably contains not more than about 16 carbon atoms.
  • the various Ys in a compound can be the same or different.
  • no Y group contains more than four carbon atoms.
  • Particularly preferred groups of compounds of the invention are those in which Het is a thiazole ring.
  • the compounds of the invention can be used alone as herbicides, for example, as dusts or granules of the compounds, or preferably they may be applied in formulations containing the active ingredients in a horticulturally acceptable extending medium.
  • the formulations are comprised of one or more active ingredients and one or more herbicidal diluents, adjuvants and/or carriers. Specific formulations are useful to facilitate the application of the compounds and to achieve specific biological objectives such as controlling the availability of the herbicide, improving adherence to plants, and the like, as is well known to those skilled in the art.
  • a presently especially preferred herbicidal compound of this inventon is 2-trifluoromethanesulfonamidothiazole.
  • the compounds of this invention are broadly active as herbicides. However, many of the compounds of this invention also show various types of plant growth modifying activity. Plant growth modification as defined herein consists of all deviations from natural development, for example, defoliation, stimulation, stunting, retardation, desiocation, tillering, dwarfing, regulation and the like. This plant growth modifying activity is generally observed as the compounds of the invention begin to interfere with certain processes within the plant. If these processes are essential, the plant will die it treated with a sufiicient dose of the compound. 'However, the type of growth modifying activity observed varies among types of plants. It has been found that with certain compounds of the invention, herbicidal activity can be separated from certain other plant growth modifying activities by controlling the rate of application.
  • Q is a halogen or perfluoroalkanesulfonate residue
  • B is an organic or inorganic base which acts as an acid acceptor and R Het, Y and n are as defined above.
  • a solution of the appropriate primary amine of Formula II and an equimolar quantity of a suitable acid acceptor such as triethylamine, dimethylaniline, pyridine and the like
  • a suitable acid acceptor such as triethylamine, dimethylaniline, pyridine and the like
  • an acid acceptor is not always necessary, and an excess of the primary amine may also serve as acid acceptor.
  • suitable solvents are 1,2-dimethoxyethane, benzene, chloroform, dichloromethane, dimethylacetamide, dimethylformamide and the like.
  • an excess of the primary amine or the acid acceptor may serve as a solvent or the reaction may be carried out in the absence of solvent.
  • an equimolar quantity of the appropriate perfiuoroalkanesulfonic anhydride or halide is added to the solution.
  • the addition is advantageously carried out at -15 C. to 100 C., and for some reactants higher or lower temperatures may be preferable.
  • the reaction mixture it is advantageous to allow the reaction mixture to remain at reflux temperature for a few hours following addition.
  • Method A may also be carried out in a high pressure reactor. This technique is particularl preferred when perfiuoroalkanesulfonyl fluorides are used as reactants. These reactions are usually carried out at temperature ranges of to 150 C., but these temperature ranges may be raised or lowered, depending upon the reactants used. Such reactions are most frequently carried out without solvent, or with dimethylformamide or excess triethylamine as solvent, but other advantageous variations are possible.
  • the product is isolated by conventional methods.
  • the reaction mixture can be extracted with excess aqueous sodium hydroxide.
  • the aqueous extract is then washed with organic solvents and treated with charcoal to remove impurities.
  • Subsequent acidification of the aqueous extract with mineral acid then affords the product as an oil or solid which is distilled, sublimed, chromatographed or recrystallized as required to give pure product.
  • water-soluble solvents are used, the reaction mixture can be poured directly into aqueous mineral acids.
  • the product is then isolated by conventional extraction techniques and purified as above.
  • M is an alkali metal and Q, R Het, Y and n are as defined above.
  • An alkali metal salt of the appropriate amine is prepared by any of several conventional methods such as by reaction with'sodium naphthalene, a metal hydride such as sodium hydride, alkoxides such as potassium t-butoxide in protic or aprotic solvents, or by reaction with an alkali metal such as sodium or potassium directly in an appropriate solvent.
  • the resulting salt is then treated with a perfiuoroalkanesulfonyl alkylating agent such as trifiuoromethanesulfonyl fluoride or chloride or trifluoromethanesulfonic anhydride, either at atmospheric pressure in open apparatus or under pressure in a pressure vessel.
  • a perfiuoroalkanesulfonyl alkylating agent such as trifiuoromethanesulfonyl fluoride or chloride or trifluoromethanesulfonic anhydride, either at atmospheric pressure in open apparatus or under pressure in a pressure vessel.
  • the reaction takes place at 0 to C., depending on the reactivity of the amine and the sulfonyl halide.
  • the product is obtained by conventional work-up techniques as described in Method A.
  • R SO NHZ XHet-Y RgSOgNH-He tY ZX (Formula III)
  • R Y, n and Het are as defined above, X is halogen and Z is an alkaline earth or alkali metal.
  • the perfiuoroalkanesulfonamide salt and an appropriate halide of Formula III are reacted, generally in a suitable solvent (such as dimethylsulfoxide, dimethylformamide, 1,2 dimethoxyethane, dimethylacetamide and the like). Heating or cooling, usually the former, may be advantageous to obtain a desirable rate of reaction.
  • the product is isolated by conventional methods. For example, when the reaction mixture is diluted with water the product may precipitate. Alternatively, the product may be extracted from the reaction mixture after dilution with water. Other recovery techniques are well known to those skilled in the art.
  • the reaction of Method C may also high pressure reactor.
  • Method C is usually most valuable when the halide is activated by suitable electron-withdrawing groups on the ring, as is well known to the art.
  • Suitable halides for use in Method C are well known to the art, as are salts of perfluoroalkanesulfonamides.
  • Suitable perfluorocarbonsulfonyl anhydrides and halides e.g. chlorides and fluorides
  • halides e.g. chlorides and fluorides
  • the amines used in producing the compounds of this invention are described in the general chemical literature or may be prepared by methods known to those skilled in the art.
  • Methods A, B and C are generally applicable (preferably Method A) to the preparation of compounds of the invention.
  • compounds wherein Y is nitro may be reduced by conventional methods to obtain compounds wherein Y is amino.
  • 2-amino-4-methylpyridine (54.1 g., 0.50 mole), triethylamine (250 ml.) and trifluoromethanesulfonyl fluoride (76.1 g., 0.50 mole) were heated at 90 C. for about one day. To this mixture was added excess sodium hydroxide percent) and the mixture was steam distilled to remove triethylamine. The residue was treated with decolorizing charcoal, filtered, then acidified with concentrated hydrochloric acid. The solid product was collected by filtration, recrystallized from isopropanol then sublimed to give N-[2-(4-methylpyridyl)]trifluoromethanesulfonamide, M.P. 220.5-222 C.
  • N-(4-pyridyl)trifluoromethanesulfonamide 310-313 15- N-(3-pyridyDtrifiuoromethanesulfonamide 240-242 16.
  • N-[2-(5 aminopyridyl)]trifluoromethanesulfonamide (12 g., 0.05 mole), acetyl chloride (3.92 g., 0.050 mole) and triethylamine (5.1 g., 0.05 mole) in benzene ml.) were stirred overnight.
  • the volatile portions were removed in vacuo and the residue recrystallized from a water-ethanol mixture to give N-[Z-(S-acetamidopyridyl)] trifiuoromethanesulfonamide, M.P. 266-267.5 C.
  • N-(2 thiazolyl)trifiuoromethanesulfonamide (25.6 g., 0.10 mole) was mixed with percent ethanol (300 ml.) and water (50 ml.) and bromine (32.0 g., 0.2 mole) was added dropwise with stirring. The reaction was stirred at room temperature for two hours, then warmed to 50 C. for thirty minutes. The reaction mixture was added to ice water (1.5 l.) and the product collected by filtration. Recrystallization from benzene gave N-[2-(5-bromothiazolyl)]trifiuoromethanesulfonamide, M.P. 195.3l98 C.
  • R is CF 3.
  • cmsomnwt TY wherein Y is halogen, and metal, ammonium and organic amine salts thereof.

Abstract

N-SUBSTITUTED PERFLUOROALKANESULFONAMIDES IN WHICH THE SOLUFONAMIDE NITROGEN SUBSTITUENT IS A HETEROATOM-CONTAINING GROUP SELECTED FROM PYRIDINYL, QUINOLINYL, PYRAZOLYL, THIAZOLYL, QUINOXALINYLPHENYL, IMIDAZO(1,2A)PYRIDINYLPHENYL, IMIDAZO(1,2A)PYRIMIDYLPHENYL AND BENZOXAZOLYL WHICH CAN BE UNSUBSTITUTED OR WHICH CAN CARRY CERTAIN SUBSTITUENTS. ALSO INCLUDED ARE SALTS OF THESE COMPOUNDS, COMPOSITIONS CONTAINING THE COMPOUNDS OF THE PRESENT INVENTION AND PROCESSES FOR THEIR PREPARATION AND USE. THE COMPOUNDS ARE ACTIVE AS HERBICIDES AND PLANT GROWTH MODIFIERS.

Description

3,801,588 CERTAIN PERFLUOROALKYLSULFON- AMIDOTHIAZOLES Joseph Kenneth Harrington, Edina, Donald C. Kvam, North Oaks, Arthur Mendel, Vadnais Heights, and Jerry E. Robertson, North Oaks, Minn., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn.
No Drawing. Continuation-impart of application Ser. No. 837,932, June 30, 1969, now Patent No. 3,637,729, which is a continuation-in-part of abandoned application Ser. No. 588,338, Oct. 21, 1966. This application May 11, 1971, Ser. No. 142,381
Int. Cl. C07d 91/26 US. Cl. 260-306.8 R 4 Claims ABSTRACT OF THE DISCLOSURE N-substituted perfluoroalkanesulfonamides in which the sulfonamide nitrogen substituent is a heteroatom-containing group selected from pyridinyl, quinolinyl, pyrazolyl, thiazolyl, quinoxalinylphenyl, imidazo[l,2a]pyridinylphenyl, imidazo[l,2a]pyrimidylphenyl and benzoxazolyl which can be unsubstituted or which can carry certain substituents.
Also included are salts of these compounds, compositions containing the compounds of the present invention and processes for their preparation and use. The compounds are active as herbicides and plant growth modifiers.
This application is a continuation-in-part of application Ser. No. 837,932, filed June 30, 1969, now US. 3,637,729, Ser. No. 837,932 being in turn a continuation-in-part of application Ser. No. 588,338 filed Oct. 21, 1966, now abandoned.
The invention relates to perfiuoroalkanesulfonamides, N-substituted by heterocyclic ring-containing groups, said compounds having activity as herbicides and plant growth modifiers, and particularly as preemergence herbicides.
Perfluoroalkanesulfonamides have been disclosed broadly heretofore (see, for example, US. Pats. 2,732,398 and 3,321,445) but there has been no indication of any herbicidal activity of such compounds.
In the N-substituted perfluoroalkanesulfonamides of the present invention, the sulfonamide nitrogen substituent is a heterocyclic ring-containing group selected from pyridinyl, quinolinyl, pyrazolyl, thiazolyl, quinoxalinylphenyl, imidazo[1,2a] pyridinylphenyl, imidazo[l,2a] pyrimidylphenyl and benzoxazolyl, said groups being unsubstituted or substituted. The invention also includes salts of the compounds, processes for their preparation, compositions containing them and methods for their use as herbicides, and plant growth modifiers.
It is an object of the invention to provide compounds which modify the growth of plants, i.e. compounds which prevent, alter, destroy or otherwise affect the growth of plants.
It is a further object of the invention to provide a method for controlling unwanted plants.
It is another object of the invention to provide herbicidal compositions containing one or more perfl-uoroalk-anesulfonamides as active ingredients therein. 1
Still other objects of the invention will be made apparent by the following specification.
DETAILED DESCRIPTION According to the present invention, there is provided a class of compounds consisting of perfiuoroalkanesulfonamides having the general formula:
United States Patent O and metal, ammonium and organic amine salts thereof wherein R, is a perfluoroalkyl group containing one to four carbon atoms, Het is selected from pyridinyl, quinolinyl, pyrazolyl, thiazolyl, quinoxalinylphenyl, imidazo- 1,2a] pyridinylphenyl, imidazo[ 1,2a] pyrimidylphenyl and benzoxazolyl, Y is lower alkyl, halogen, cyano, lower alkoxy, nitro, amino or lower alkanolylamido and n is 0- 2 when Het is thiazolyl and is otherwise 03. When n is zero, the Het group in the compound is not substituted by any Y groups, i.e. hydrogen appears in place of the Y groups. The compounds of the invention in which n is 0 or, in which n is 1 form preferred classes of compounds of the invention.
In the metal, ammonium and organic amine salts, the sulfonamide hydrogen of the formula is replaced by a suitable cation.
The salts of the invention are prepared by treating the acid form (shown in the foregoing Formula I) with a stoichiometrically equivalent amount of an appropriate base under mild conditions. Among the metal salts of the invention are alkali metal (e.g. lithium, sodium and potassium), alkaline earth metal (e.g. barium, calcium and magnesium) and heavy metal (e.g. zinc and iron) salts as well as other metal salts such as aluminum. Appropriate bases for use in preparing the metal salts include metal oxides, hydroxides, carbonates, bicarbonates and alkoxides. Some salts are also prepared by transmetallation reactions. The organic amine salts include the salts of alkylamines and aromatic amines, primary, secondary or tertiary. These and the ammonium salts can be prepared by reacting the acid form with the appropriate organic base or ammonium hydroxide. The salts of the invention are frequently formed by reacting the precursors in aqueous solution. This solution can be evaporated to obtain the salt of the compound usually as a dry powder. In some cases, it may be more convenient to use a non-aqueous solvent such as alcohols, acetone, etc. Since many of the salts are water soluble, they are often used in the form of aqueous solutions.
Due to the acidity of the hydrogen of the sulfonamido group of Formula I, the compounds of the invention are catalysts for certain acid-catalyzed polymerizations. Many of the compounds of the invention are anti-microbial agents, according to standard test procedures. Also, some are anti-inflammatory agents when tested by standard test procedures using animals.
Preferably, R; in the compounds of the invention is trifiuoromethyl. Price is an important consideration in herbicides and such compounds offer more economical utilization of fluorine together with high activity. The group Het-Yn in the compounds usually and preferably contains not more than about 16 carbon atoms. The various Ys in a compound can be the same or different. Preferably, no Y group contains more than four carbon atoms. Particularly preferred groups of compounds of the invention are those in which Het is a thiazole ring.
In order to control unwanted plants, the compounds of the invention can be used alone as herbicides, for example, as dusts or granules of the compounds, or preferably they may be applied in formulations containing the active ingredients in a horticulturally acceptable extending medium. The formulations are comprised of one or more active ingredients and one or more herbicidal diluents, adjuvants and/or carriers. Specific formulations are useful to facilitate the application of the compounds and to achieve specific biological objectives such as controlling the availability of the herbicide, improving adherence to plants, and the like, as is well known to those skilled in the art.
A presently especially preferred herbicidal compound of this inventon is 2-trifluoromethanesulfonamidothiazole.
Patented Apr. 2, 1974 The compounds of this invention are broadly active as herbicides. However, many of the compounds of this invention also show various types of plant growth modifying activity. Plant growth modification as defined herein consists of all deviations from natural development, for example, defoliation, stimulation, stunting, retardation, desiocation, tillering, dwarfing, regulation and the like. This plant growth modifying activity is generally observed as the compounds of the invention begin to interfere with certain processes within the plant. If these processes are essential, the plant will die it treated with a sufiicient dose of the compound. 'However, the type of growth modifying activity observed varies among types of plants. It has been found that with certain compounds of the invention, herbicidal activity can be separated from certain other plant growth modifying activities by controlling the rate of application.
Broadly speaking, the compounds of this invention are readily prepared by one or all of the following methods, each of which is illustrated by an equation.
where Q is a halogen or perfluoroalkanesulfonate residue, B is an organic or inorganic base which acts as an acid acceptor and R Het, Y and n are as defined above.
A solution of the appropriate primary amine of Formula II and an equimolar quantity of a suitable acid acceptor (such as triethylamine, dimethylaniline, pyridine and the like) in an inert organic solvent is ordinarily used. However, an acid acceptor is not always necessary, and an excess of the primary amine may also serve as acid acceptor. Among the suitable solvents are 1,2-dimethoxyethane, benzene, chloroform, dichloromethane, dimethylacetamide, dimethylformamide and the like. Alternatively, an excess of the primary amine or the acid acceptor may serve as a solvent or the reaction may be carried out in the absence of solvent. Generally, an equimolar quantity of the appropriate perfiuoroalkanesulfonic anhydride or halide is added to the solution. The addition is advantageously carried out at -15 C. to 100 C., and for some reactants higher or lower temperatures may be preferable. In cases where the amine is of lower reactivity, it is advantageous to allow the reaction mixture to remain at reflux temperature for a few hours following addition.
The reaction of Method A may also be carried out in a high pressure reactor. This technique is particularl preferred when perfiuoroalkanesulfonyl fluorides are used as reactants. These reactions are usually carried out at temperature ranges of to 150 C., but these temperature ranges may be raised or lowered, depending upon the reactants used. Such reactions are most frequently carried out without solvent, or with dimethylformamide or excess triethylamine as solvent, but other advantageous variations are possible.
It will be appreciated that the scope of this invention encompasses starting materials of a wide range of physical and chemical properties, and the synthetic methods A, B and C discussed herein are described in general and preferred language. However, a great variation in the use of these synthetic techniques is possible, and this invention is broadly inclusive of such variations.
After completion of the reaction, the product is isolated by conventional methods. For example, the reaction mixture can be extracted with excess aqueous sodium hydroxide. The aqueous extract is then washed with organic solvents and treated with charcoal to remove impurities. Subsequent acidification of the aqueous extract with mineral acid then affords the product as an oil or solid which is distilled, sublimed, chromatographed or recrystallized as required to give pure product. When water-soluble solvents are used, the reaction mixture can be poured directly into aqueous mineral acids. The product is then isolated by conventional extraction techniques and purified as above.
where M is an alkali metal and Q, R Het, Y and n are as defined above.
An alkali metal salt of the appropriate amine is prepared by any of several conventional methods such as by reaction with'sodium naphthalene, a metal hydride such as sodium hydride, alkoxides such as potassium t-butoxide in protic or aprotic solvents, or by reaction with an alkali metal such as sodium or potassium directly in an appropriate solvent.
The resulting salt is then treated with a perfiuoroalkanesulfonyl alkylating agent such as trifiuoromethanesulfonyl fluoride or chloride or trifluoromethanesulfonic anhydride, either at atmospheric pressure in open apparatus or under pressure in a pressure vessel. The reaction takes place at 0 to C., depending on the reactivity of the amine and the sulfonyl halide. On completion of the reaction, the product is obtained by conventional work-up techniques as described in Method A.
Method C R SO NHZ XHet-Y RgSOgNH-He tY ZX (Formula III) R Y, n and Het are as defined above, X is halogen and Z is an alkaline earth or alkali metal. The perfiuoroalkanesulfonamide salt and an appropriate halide of Formula III are reacted, generally in a suitable solvent (such as dimethylsulfoxide, dimethylformamide, 1,2 dimethoxyethane, dimethylacetamide and the like). Heating or cooling, usually the former, may be advantageous to obtain a desirable rate of reaction.
After the completion of the reaction, the product is isolated by conventional methods. For example, when the reaction mixture is diluted with water the product may precipitate. Alternatively, the product may be extracted from the reaction mixture after dilution with water. Other recovery techniques are well known to those skilled in the art.
The reaction of Method C may also high pressure reactor.
Method C is usually most valuable when the halide is activated by suitable electron-withdrawing groups on the ring, as is well known to the art. Suitable halides for use in Method C are well known to the art, as are salts of perfluoroalkanesulfonamides.
Suitable perfluorocarbonsulfonyl anhydrides and halides (e.g. chlorides and fluorides) for use in these procedures are known to the art (thus see US. Pat. 2,732,398). Similarly, the amines used in producing the compounds of this invention are described in the general chemical literature or may be prepared by methods known to those skilled in the art.
Methods A, B and C are generally applicable (preferably Method A) to the preparation of compounds of the invention. However, it is sometimes preferable, in order to increase yields and minimize purification problems, to utilize compounds of the invention in conventional, known procedures to prepare other compounds of the invention. For example, compounds wherein Y is nitro may be reduced by conventional methods to obtain compounds wherein Y is amino.
The following examples are given for the purpose of further illustrating the procedures of the present invention, but are not intended, in any way, to be limiting on the scope thereof. Thus while the examples relate to perfluoromethanesulfonamides, other perfluorocarbon groups can be substituted in place thereof. Also, although the be carried in a examples relate for the most part to compounds in the acid form (that is having a hydrogen atom bonded to the amide nitrogen), it is understood that the corresponding salts of the invention are also easily prepared and are likewise contemplated. Such salts, which have a cation bonded to the sulfonamide nitrogen, are also useful as herbicides, and in some cases as plant growth modifiers.
EXAMPLE 1 This preparation was carried out using Method A as follows:
2-amino-4-methylpyridine (54.1 g., 0.50 mole), triethylamine (250 ml.) and trifluoromethanesulfonyl fluoride (76.1 g., 0.50 mole) were heated at 90 C. for about one day. To this mixture was added excess sodium hydroxide percent) and the mixture was steam distilled to remove triethylamine. The residue was treated with decolorizing charcoal, filtered, then acidified with concentrated hydrochloric acid. The solid product was collected by filtration, recrystallized from isopropanol then sublimed to give N-[2-(4-methylpyridyl)]trifluoromethanesulfonamide, M.P. 220.5-222 C.
Analysis.--Calcd. for C H F N O S (percent): C, 35.0; H, 2.9; N, 11.7. Found (percent): C, 35.0; H, 2.9; N, 11.9.
The following table lists compounds of the invention prepared according to Method A as described above.
Ex. M.P
No. Compound C 2... N-[2- (5-bromopyrldylltrlfiuoromethanesu1ionamide-- 238. 5-240 3-- N-(Z-pyridyl)trifluoromethanesulfonamide 222-223 4. N- (8-qu1nolinyl) trifluoromethanesulionamide 143. 5-145 5- N-[3-(5-methylpyrazolyl)ltrifluoro- 206. 5-212. 5
methanesulfonamide.
6.- 4-(2-quinoxalinyl)trifluoromethanesullonanilide 227-231 7. N-(Z-thiazolyl)trifluoromethanesultonamide 202-205 8. 2-(4-trifluoromethylsulfonamidophenyl)imidazo- 254-259 [1,2a] pyridine.
9. 1,3,5-trimethyl-4-trifluoromethyl- 166-168 5 sulfonamidopyrazole.
10..-. 5-cyan0-1,3-dimethyl-4-tflfluoromethyl- 149-151 sulfonamidopyrazole.
11.- N-[3-(2,6dimethoxypyridyl)]trifluoro- 89. 5-91 methanesulfon e.
12. N-[5-(2-methoxypyrldyl)]trifluoro- 144. 5-146. 5
methanesulfonamide.
13-- N-[2-(6-methylpyridyl)]trifiuoro- 167-168 methanesulfonamide.
14. N-(4-pyridyl)trifluoromethanesulfonamide 310-313 15- N-(3-pyridyDtrifiuoromethanesulfonamide 240-242 16. N-[4-(3-brom0pyridyl)]trifluoro- 173. 5-175. 5
methanesulionamide.
17. N-[2-(5-nitropyridyl)ltrifluoromethanesulfonamide. 235-236 5 methanesulfonamide.
19- N-[5-(2-n-butoxypyridyl)]tr1fiuoro- 84. 5-86. 5
methanesulionarni e.
20- N-[2-(4,6-dimethylpyrldyl)]trifluoro- 127-128 methanesulionamide.
21.- 2-(4-trifluoromethylsu1fonamidophenyl) 250 imidazo[1,2a]pyrimidine.
EXAMPLE 22 This preparation was carried out using Method C as follows:
A solution of trifluoromethanesulfonamide (14.9 g., 0.10 mole) in dimethylformamide was treated with 1 equivalent of sodium hydride and the mixture added at room temperature to 15.3 g. of 2-chlorobenzoxazole in dimethylformamide. The reaction mixture was heated with stirring for 2 hours at 80 C. and poured into 600 mls. of aqueous sodium hydroxide. The aqueous layer was washed with ether and acidified with hydrochloric acid. A white solid precipitated. Recrystallization from aqueous ethanol afforded an analytical sample of N(2-benzoxazolyl)trifluoromethanesulfonamide, M.P. 197.5-198" C.
Analysis.Calcd. for C H F N O S (percent): C, 36.1; H, 1.9. Found (percent): C, 36.2; H, 1.9.
EXAMPLE 23 N-[2 (5 nitropyridyl)]trifiuoromethanesulfonamide (20 g., 0.074 mole) in ethanol (250 ml.) was reduced over palladium on charcoal with hydrogen gas. The catalyst was removed by filtration and the ethanol evaporated in vacuo to give N-[Z-(S-aminopyridyl)]trifluoromethanesulfonamide.
N-[2-(5 aminopyridyl)]trifluoromethanesulfonamide (12 g., 0.05 mole), acetyl chloride (3.92 g., 0.050 mole) and triethylamine (5.1 g., 0.05 mole) in benzene ml.) were stirred overnight. The volatile portions were removed in vacuo and the residue recrystallized from a water-ethanol mixture to give N-[Z-(S-acetamidopyridyl)] trifiuoromethanesulfonamide, M.P. 266-267.5 C.
Analysis.-Calcd. for C H F N 0 S: (percent): C, 33.9; H, 2.9; N, 14.8. Found (percent): C, 34.0; H, 2.8; N, 15.0. I
EXAMPLE 24 N-(2 thiazolyl)trifiuoromethanesulfonamide (25.6 g., 0.10 mole) was mixed with percent ethanol (300 ml.) and water (50 ml.) and bromine (32.0 g., 0.2 mole) was added dropwise with stirring. The reaction was stirred at room temperature for two hours, then warmed to 50 C. for thirty minutes. The reaction mixture was added to ice water (1.5 l.) and the product collected by filtration. Recrystallization from benzene gave N-[2-(5-bromothiazolyl)]trifiuoromethanesulfonamide, M.P. 195.3l98 C.
Analysis.Calcd. for C H Br F N O S (percent): C, 15.4; H, 0.6; N, 9.0. Found (percent): C, 15.6; H, 0.7; N, 9.1.
EXAMPLE 25 N-(Z-thiazolyl)trifiuorornethanesulfonamide (25 g., 0.1 mole) in carbon disulfide (250 ml.) was heated to reflux temperature and maintained there while adding sulfuryl chloride (50 g., 0.37 mole) in carbon disulfide (100 ml.) dropwise during three hours with vigorous stirring. Reflux and stirring were continued twelve hours. More sulfuryl chloride (50 g.) was added and refluxing was carried out intermittently for several days for a total of twenty-four hours. A solid product was obtained by cooling and collooted by filtration, then recrystallized from benzene-ethanol to give N-[2-(5 chlorothiazolyl)]trifluoromethanesulfonarnide, M.P. 167-168" C.
Analysis.--Calcd. for C H ClF N O S (percent): C, 18.0; H, 0.8; N, 10.5. Found (percent): C, 18.2; H, 0.7; N, 10.3.
EXAMPLE 26 Representative salts of the invention which have been prepared are:
Sodium N-(2-pyridyl)trifluoromethanesulfonamide (partially purified sample decomposes -165 C.).
Zinc N-(8-quinolinyl)trifluoromethansulfonamide 9 N-SOgCF;
CFgSOzN M.P. greater than 300 C.
7 What is claimed is: 1. A compound of the formula:
R SO NHHetY and metal, ammonium and organic amine salts thereofi 5 10 2. A compound according to claim 1 in which R, is CF 3. A compound according to claim 2 of the formula:
cmsomnwt TY wherein Y is halogen, and metal, ammonium and organic amine salts thereof.
4. The compound Z-trifluoromethanesulfonamidothiazole.
References Cited UNITED STATES PATENTS 3,637,729 1/ 1972 Harrington et a1. 260306.8 R
RICHARD J. GALLAGHER, Primary Examiner US. Cl. X.R.
7'1-88, 90, 92, 94; 260242, 250 Q, 256.5 R, 270, 288 R, 294.8 C, 294.8 F, 299, 307 D, 310 R, 999
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923810A (en) * 1971-05-11 1975-12-02 Minnesota Mining & Mfg Perfluoroalkanesulfonamides N-substituted by heterocyclic groups
US3957812A (en) * 1973-08-29 1976-05-18 S.P.R.L. Phavic Derivatives of 2-phenoxyacetamido-5-nitro-thiazole

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923810A (en) * 1971-05-11 1975-12-02 Minnesota Mining & Mfg Perfluoroalkanesulfonamides N-substituted by heterocyclic groups
US3957812A (en) * 1973-08-29 1976-05-18 S.P.R.L. Phavic Derivatives of 2-phenoxyacetamido-5-nitro-thiazole

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